CN102674465B - Method for recycling chlorine gas from HCl-containing exhaust gas and preparing manganese chloride, and manganese chloride crystals - Google Patents
Method for recycling chlorine gas from HCl-containing exhaust gas and preparing manganese chloride, and manganese chloride crystals Download PDFInfo
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- CN102674465B CN102674465B CN201210161407.3A CN201210161407A CN102674465B CN 102674465 B CN102674465 B CN 102674465B CN 201210161407 A CN201210161407 A CN 201210161407A CN 102674465 B CN102674465 B CN 102674465B
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Abstract
The invention provides a method for recycling chlorine gas from HCl-containing exhaust gas and preparing manganese chloride, and manganese chloride crystals. The method comprises the following steps: 1. introducing HCl-containing exhaust gas into MnO2 pulp to carry out reaction, stopping the reaction when the pH value of the pulp reaches 1-2, wherein the concentration of MnCl2 in the pulp after the reaction is stopped is controlled at 100-300g/L, and meanwhile, the Cl2-containing gas after the reaction is recycled; 2. carrying out solid-liquid separation on the pulp obtained in the step 1 to obtain a first filtrate, adding manganese-containing alkali liquor into the first filtrate for neutralization until the pH value reaches 3-3.5, removing impurities, and filtering to obtain a second filtrate; and 3. crystallizing the second filtrate, and recrystallizing to obtain the MnCl2.4H2O product. The method can be used for preparing the manganese chloride product which satisfies the following condition required by a lithium ion secondary battery: on the basis of MnCl2.4H2O, the purity is higher than 99.71%.
Description
Technical field
The present invention relates to a kind of method of the vent gas treatment containing HCl, especially relate to a kind of utilization containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate.
Background technology
Domestic titanium sponge industry and organic chloride production industry all discharge relatively large containing HCl tail gas.Prior art to containing the treatment process of HCl tail gas for making by-product hydrochloric acid, or with alkali liquor absorption, contain HCl tail gas and processed.But all there is certain defect in above two kinds for the treatment of processs, for example in by-product hydrochloric acid, foreign matter content is high, adds the seasonal demand of by-product hydrochloric acid is caused to environmental protecting device steady running throughout the year; Alkali liquor absorption produces a large amount of lower concentration salt solution of meeting, thereby has caused the secondary pollution of environment.
Manganous chloride tetrahydrate is the basic raw material of the products such as high-quality manganous carbonate, trimanganese tetroxide, is again the basic material of ternary cathode material of lithium ion battery simultaneously.Manganous chloride tetrahydrate generally adds hydrochloric acid by manganese carbonate ore to be produced through purifying again, but because manganese carbonate ore impurity is high, to purification, brings larger difficulty.
Summary of the invention
Technical problem to be solved by this invention is: overcome the high and secondary pollution environment of the existing exhaust gas treating method gained salt acid product foreign matter content containing HCl, adopt manganese carbonate ore to prepare the defects such as Manganous chloride tetrahydrate Ca, Mg impurity are high, purification difficult, the tail gas recycle Cl of a kind of utilization containing HCl is provided
2and prepare the method for Manganous chloride tetrahydrate, and adopt the tail gas manganese dioxide reduction ore deposit containing HCl, reclaim Cl
2obtain highly purified Manganous chloride tetrahydrate simultaneously, solved the recycling difficulty of tail gas and the problem of value Mn reduction purification difficult containing HCl.
The present invention adopts the tail gas manganese dioxide reduction ore deposit containing HCl, reclaims Cl
2obtain manganese chloride solution simultaneously.The present invention adds manganous carbonate to regulate pH value in manganese chloride solution, then according to Fe
2+ionic weight adds manganese sulfide removal of impurities, obtained meet lithium-ion secondary cell required with MnCl
24H
2the more than 99.71% high-purity Manganous chloride tetrahydrate product of O meter purity.In the mother liquor that the present invention obtains in crystallisation step solid-liquid separation, add reaction mole NH
4hCO
3solid reacts, and has solved the problem of system impurity recycling enrichment.The present invention adopts dioxide ore for manganese to replace manganese carbonate ore as raw material, has solved manganese carbonate ore Ca, problem that Mg impurity is high.
In order to solve the problems of the technologies described above, the first technical scheme that the present invention adopts is that a kind of utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, the method comprises: first step, is passed into MnO by the tail gas containing HCl
2in slurry, react, stopped reaction when slurry pH is 1-2, and control reaction stops MnCl in disposed slurry
2concentration be 100-300g/L, contain Cl after reclaiming reaction simultaneously
2gas; Second step, obtains the first filtrate by first step gained slurry solid-liquid separation, and then in gained the first filtrate, adding alkaline substance containing manganese to be neutralized to pH is 3-3.5, and then removal of impurities, filtration, obtain the second filtrate; Third step, carries out crystallization, recrystallization processing by second step gained the second filtrate, obtains MnCl
24H
2o product.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, and in first step, described MnO
2the solid content of slurry is 300-350kg/m
3.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, in first step, adopt three grades of absorption cycles to react.In every one-level, MnO
2slurry sprays downwards, carries out redox reaction with the tail gas countercurrent flow containing HCl.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, describedly containing the tail gas of HCl and the gas-liquid volume ratio example of slurry, be controlled at 12-15L/Nm
3.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, in second step, the described alkaline substance containing manganese comprises MnCO
3, Mn (OH)
2, and basic salt, alkali, the oxide compound such as MnO.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, in second step, described removal of impurities comprises: with Fe in filtrate
2+molar weight meter, adds the MnS of 3 times of molar weights, then described the first filtrate is warmed up to 80-90 ℃, and insulation is processed to Fe
2+content be less than 2ppm.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, described crystallisation step comprises: second step gained the second filtrate is evaporated to MnCl
2concentration be 800-840g/L, be then cooled to below 35 ℃, solid-liquid separation obtains MnCl
24H
2o crystallization.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, described recrystallize step comprises: by crystallisation step gained MnCl
24H
2o crystallization is made into the supersaturated solution of 90 ℃, and under heat-retaining condition, solid-liquid separation obtains the 4th filtrate for the first time, then gained filtrate is cooled to below 35 ℃, follows solid-liquid separation, the dry MnCl that obtains for the second time
24H
2o crystallization.
Aforesaid utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, in the mother liquor that the solid-liquid separation of described crystallisation step obtains, add the NH that reacts molar weight
4hCO
3solid reacts and obtains MnCO
3, and by described MnCO
3be applied to the neutralization procedure of the first filtrate.
The second technical scheme that the present invention adopts is, a kind of Manganous chloride tetrahydrate crystallization, its MnCl
24H
2o content is greater than 99.7wt%.
Aforesaid Manganous chloride tetrahydrate crystallization, it is characterized in that, its K content < 10.0ppm, Na content < 10.0ppm, Ca content is 5.4-8.5ppm, Mg content is 3.2-6.5ppm, Fe content < 1.0ppm and Si content < 1.0ppm.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the preferred process flow sheet of the present invention.
Embodiment
For fully understanding the present invention's object, feature and effect, by following concrete embodiment, the present invention is elaborated.
The present invention adopts the tail gas manganese dioxide reduction ore deposit containing HCl, reclaims Cl
2obtain manganese chloride solution simultaneously, solved the recycling problem containing the tail gas of HCl.The present invention adds manganous carbonate to regulate pH value in manganese chloride solution, then according to Fe
2+ionic weight adds manganese sulfide removal of impurities, obtained meet lithium-ion secondary cell required with MnCl
24H
2the more than 99.71% high-purity Manganous chloride tetrahydrate product of O meter purity.
Tail gas containing HCl of the present invention refers to the tail gas containing HCl of titanium sponge industry and the discharge of organic chloride production industry.Titanium sponge production process comprises that smelting procedure, the titanium slag of titanium ore smelting titanium slag react the chloride process that generates crude titanic chloride with chlorine, carbon, refining step, and magnesium reduction is produced the operation of finished product titanium sponge.The tail gas that titanium sponge is produced is mainly from chloride process and refining step, mainly comprise 10-30%(v/v) chlorine and hydrogenchloride, chlorine is mainly derived from the responseless chlorine feed of chloride process, and the hydrogenchloride mainly moisture in raw material and chlorine reaction generates.Utilization of the present invention is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, be applicable to the tail gas containing HCl that titanium sponge produces in producing.
Utilization of the present invention is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, be not only applicable to the tail gas containing HCl producing in titanium sponge production, also be applicable to the tail gas containing HCl of other organic chloride production industry discharges, the tail gas containing HCl producing in the tail gas that contains HCl, the tail gas containing HCl producing or the aromatic substance chlorination for example, producing in the tail gas containing HCl that the tail gas that contains HCl, the acyl chlorides producing in phosgene and amine reaction production isocyanic ester produces in producing, polycarbonate production from Ethylene Dichloride production vinyl chloride.
The present invention does not have particular requirement to the content containing HCl in the tail gas of HCl, can regulate the means such as exhaust flow by controlling the reaction times, makes HCl in tail gas meet the demand of manganese dioxide reduction.
Describe utilization of the present invention below in detail containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate.
A kind of utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, the method comprises the steps.
First step, contains the absorption of the tail gas of HCl
Tail gas containing HCl is passed into MnO
2in slurry, react, stopped reaction when slurry pH is 1-2, and control reaction stops MnCl in disposed slurry
2concentration be 100-300g/L, contain Cl after reclaiming reaction simultaneously
2gas.
Preferably, in first step, the main chemical reactions of generation is: 4HCl+MnO
2→ Cl
2↑+MnCl
2+ 2H
2o.
In first step, described MnO
2slurry is by MnO
2breeze adopts ordinary method formulated, the MnO of various grades
2breeze all can be applicable to the present invention.Described MnO
2the solid content of slurry is controlled as reacting and is stopped MnCl in disposed slurry
2concentration be 100～300g/L, preferred MnO
2breeze grade is Mn content while being 14wt%-42wt%, MnO
2the solid content of slurry is 350-300kg/m
3, MnO for example
2breeze grade is Mn content while being 14wt%, MnO
2the solid content of slurry is 350kg/m
3, reaction stops MnCl in disposed slurry
2concentration be about 112g/L; MnO
2breeze grade is Mn content while being 40wt%, MnO
2the solid content of slurry is 330kg/m
3, reaction stops MnCl in disposed slurry
2concentration be about 300g/L.
The tail gas containing HCl of the preferred titanium sponge industry discharge of the described tail gas containing HCl, mainly comprises 10-30%(v/v) chlorine and hydrogenchloride.
Preferably, in first step, the present invention is containing tail gas and the MnO of HCl
2slurry carries out the reaction of gas-liquid two-phase countercurrent spray.Preferred the present invention for example, carries out the reaction of gas-liquid two-phase countercurrent spray in multistage absorption device (three grades of absorption units).Concrete, every grade of absorption unit is: average gas flow 24000-27000Nm
3/ h, gas-liquid volume ratio example is controlled at 12-15L/Nm
3first in the first step circulatory pool of absorption unit, pass into the tail gas containing HCl, the part not absorbed by slurry in first step absorption unit containing the tail gas of HCl flows into second stage absorption unit circulatory pool, in the absorption unit of the second stage, by slurry absorption portion, is not flowed into third stage absorption unit circulatory pool, and then is discharged containing higher concentration Cl by third stage absorption unit
2tail gas, this tail gas further enters concentration unit recycling.Adopt conventional pumps feed technique, by MnO
2slurry pumping is to the third stage circulatory pool of absorption unit, and controls it and do countercurrent flow with respect to the tail gas containing HCl.Three grades of circulatory pools of these three grades of absorption units carry out separately respectively self-circulation, in the first step, the second stage and third stage circulatory pool, spray respectively slip downwards, after the discharging of first step circulatory pool, slurry pumping in the circulatory pool of the second stage is to the first step, slurry pumping in third stage circulatory pool is to the second stage, and third stage circulatory pool enters new slurry.The condition of above-mentioned first step circulatory pool discharging is that in first step absorption unit circulatory pool, the pH of the slurry of spray is 1-2 downwards.
The tail gas that the present invention passes into containing HCl carries out spray-absorption reaction, and it is airtight that absorption unit needs, so the mode that ventage adopts lime solution to carry out water seal seals, to prevent Cl
2reveal.The mode that the present invention preferably adopts every grade of absorption unit to have two circulatory pools turns round, and to shorten switching time, guarantees assimilated efficiency.
Second step, separation, neutralization, removal step
First step gained slurry solid-liquid separation is obtained to filtrate (I), and then in filtrate (I), adding alkaline substance containing manganese to be neutralized to pH is 3-3.5, and then removal of impurities, filtration, obtain filtrate (II).The described alkaline substance containing manganese comprises MnCO
3, Mn (OH)
2, and basic salt, alkali, the oxide compound such as MnO.
In second step, the main chemical reactions of generation is: MCl
2+ MnS → MS+MnCl
2(M-Cn, Zn, Pb, Fe etc.).
Preferably, in second step, adopt the conventional solid-liquid separation means such as press filtration separation to carry out separation to first step gained slurry, filter residue washes with water, and washing lotion is returned to MnO
2breeze operation with slurry is used, and residue is abandoned.
Preferably, in second step, described removal of impurities is treated to: solid-liquid separation gained filtrate (I) is measured to Fe
2+molar weight, record Fe
2+content be 7000-15000ppm.Be incorporated as Fe
2+the MnS solid of 3 times of molar weights, then described filtrate is warmed up to 80-90 ℃, under agitation condition, insulation is processed to Fe
2+content be less than 2ppm, preferably 3-5 hour is processed in insulation.
Preferably, in second step, filtrate solid-liquid separation (preferably press filtration), secondary filter (preferably 0.5 μ m filter membrane) after removal of impurities is processed obtain filtrate (II), and filter cake is used for reclaiming valuable metal Cu, Zn, Pb, Fe etc.
Third step, crystallization, re-crystallization step
Second step gained filtrate (II) is carried out to crystallization, recrystallize processing, obtain MnCl
24H
2o product.
Preferably, in third step, described crystallisation step comprises: second step gained filtrate (II) is evaporated to MnCl
2concentration be 800-840g/L, then under agitation condition, be cooled to below 35 ℃, solid-liquid separation obtains MnCl
24H
2o crystallization.
Preferably, in third step, described re-crystallization step comprises: by gained MnCl
24H
2o crystallization is made into the supersaturated solution of 90 ℃ with deionized water, under heat-retaining condition, solid-liquid separation obtains filtrate (IV) for the first time, then under agitation condition, gained filtrate is cooled to below 35 ℃, follows solid-liquid separation, the dry MnCl that obtains for the second time
24H
2o crystallization.Solid-liquid separation filtrate (V) is returned to the evaporization process of crystallisation step for the second time.Conventional crystal drying means all can be applicable to the present invention, preferably vibra fluidized bed drying.
Preferably, in third step, in the mother liquor (III) that the solid-liquid separation of described crystallisation step obtains, add the NH of reaction mole
4hCO
3solid reacts, solid-liquid separation (preferably press filtration separated) then, and filtrate is reclaimed NH
4cl, filter cake MnCO
3can be in second step and operation, unnecessary MnCO
3can add to MnO
2operation with slurry.The main chemical reactions that this step occurs is: MCl
2+ MnS → MS+MnCl
2(M-Cu, Zn, Pb, Fe etc.).
The mother liquor that crystallisation step solid-liquid separation of the present invention obtains add reaction mole NH
4hCO
3solid reacts, and makes directly exhaust emission environment or loop back technique of the present invention and cause system impurity enriched of this mother liquor, and by adding the NH of reaction mole
4hCO
3solid reacts and has reclaimed NH
4during Cl and having obtained can be applied to and the MnCO of operation
3.
The invention provides a kind of Manganous chloride tetrahydrate, its MnCl
24H
2o content is greater than 99.7wt%.Preferably, this Manganous chloride tetrahydrate kind, K content < 10.0ppm, Na content < 10.0ppm, Ca content is 5.4-8.5ppm, and Mg content is 3.2-6.5ppm, Fe content < 1.0ppm and Si content < 1.0ppm.
Below by specific embodiment, set forth the enforcement of method of the present invention, one skilled in the art will appreciate that this should not be understood to the restriction to the claims in the present invention scope.
Embodiment
First, to utilizing the tail gas recycle Cl containing HCl in embodiment below
2and determinator and measuring method used is described as follows when preparing the preparation process of Manganous chloride tetrahydrate and product and analyzing:
Fe
2+detection method: inductively coupled plasma (ICP) atomic emission spectrometry
Mn
2+detection method: inductively coupled plasma (ICP) atomic emission spectrometry
MnCl
24H
2o detection method of content: measure according to the ammonium nitrate oxidation reduction method in standard HGT3816-2006.
Product elemental analysis method: inductively coupled plasma (ICP) atomic emission spectrometry
Fe<sup TranNum="255">2+</sup>with product Atomic Absorption SpectrophotometerICP: IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, U.S. power & light company system;
PH value determinator: PHS-3C type precision acidity meter, Shanghai precision instrumentation company system.
HCl and Cl in tail gas in the present embodiment
2measuring method adopt HCl and Cl in conventional tail gas
2measuring method.
Embodiment 1
Adopt the low-grade MnO that Mn content is 16.23wt%
2breeze is as raw material, and to be mixed with solid content be 350Kg/m
3slurry.Adopt titanium sponge produce in the tail gas containing HCl of discharge be raw material, this tail gas mainly comprises 14.71%(v/v) chlorine and hydrogenchloride, wherein chlorine is approximately 3-4%(v/v).
The present embodiment adopts three grades of absorption units, and the mode that ventage adopts lime solution to carry out water seal is sealed.The present embodiment technological process is as follows.
One. contain the absorption of the tail gas of HCl
First in the first step circulatory pool of absorption unit, pass into the above-mentioned tail gas containing HCl, average flue gas flow 24000-27000Nm
3/ h, gas-liquid volume ratio example is controlled at 12L/Nm
3.Then ON cycle pump, by above-mentioned MnO
2slurry pumping is to first and second and three grades of circulatory pools of absorption unit.Control slurry and spray downwards, slurry and tail gas counter-current operation.Slurry in first step absorption unit circulatory pool is measured, and pH is 1 o'clock, and the slurry in first step absorption unit circulatory pool is exported, MnCl in gained slurry
2concentration is 123.4g/L.Then, the slurry pumping in the circulatory pool of the second stage is to the first step, and the slurry pumping in third stage circulatory pool is to the second stage, and third stage circulatory pool enters new slurry, proceeds reaction.The part not absorbed by slurry in first step absorption unit containing the tail gas of HCl flows into second stage absorption unit circulatory pool, in the absorption unit of the second stage, by slurry absorption portion, is not flowed into third stage absorption unit circulatory pool, Cl in the tail gas that third stage circulatory pool is discharged
2concentration be 8.36%(v/v).
Two. separation, neutralization, removal of impurities
Adopt press filtration separation to carry out separation to the slurry of deriving in first step absorption unit circulatory pool, gained filter residue washes with water, and washing lotion is returned to MnO
2breeze operation with slurry is used, and residue is abandoned.Gained filtrate (I) is used MnCO
3neutralization is 3 to pH.
Sampling records the Fe in filtrate
2+content be 7000ppm, according to Fe
2+3 times of molar weights, in filtrate, add MnS solid, then this filtrate is warmed up to 90 ℃, under 50 revs/min of agitation conditions, insulation was processed after 5 hours, sampling records Fe in filtrate
2+content be less than 2ppm, stop stirring.Above-mentioned filtrate is carried out to secondary filter with 0.5 μ m filter membrane, obtain filtrate (II).
Three. crystallization
Filtrate (II) is positioned in evaporating pan, is evaporated to MnCl in filtrate
2concentration be 800g/L, then under 50 revs/min of agitation conditions, be cooled to 33 ℃, stop stirring, then solid-liquid separation obtains MnCl
24H
2o crystallization.In the separated mother liquor of solid-liquid separation gained (III), add the NH that reacts molar weight
4hCO
3solid reacts, and then press filtration is separated, filter cake MnCO
3be cycled to used in filtrate (I) in and operation.
Four. recrystallization
By gained MnCl
24H
2o crystallization is made into the supersaturated solution of 90 ℃ with deionized water, under heat-retaining condition, solid-liquid separation obtains filtrate (IV), then under agitation condition, gained filtrate is cooled to 33 ℃, and then solid-liquid separation, vibra fluidized bed drying obtain MnCl
24H
2o crystallization 1#.
Embodiment 2
Adopt the middle grade MnO that Mn content is 24.04wt%
2breeze is as raw material, and to be mixed with solid content be 300Kg/m
3slurry.Adopting the tail gas containing HCl of titanium sponge industry discharge is raw material, and this tail gas mainly comprises 17.11%(v/v) chlorine and hydrogenchloride, wherein chlorine is approximately 3-4%(v/v).
The present embodiment adopts three grades of absorption units, and the mode that ventage adopts lime solution to carry out water seal is sealed.The present embodiment technological process is as follows.
One. contain the absorption of the tail gas of HCl
First in the first step circulatory pool of absorption unit, pass into the above-mentioned tail gas containing HCl, average flue gas flow 24000-27000Nm
3/ h, gas-liquid volume ratio example is controlled at 13.5L/Nm
3.Then ON cycle pump, by above-mentioned MnO
2slurry pumping is to first and second and three grades of circulatory pools of absorption unit.Control slurry and spray downwards, slurry and tail gas counter-current operation.Slurry in first step absorption unit circulatory pool is measured, and pH is 1.5 o'clock, and the slurry in first step absorption unit circulatory pool is exported, MnCl in gained slurry
2concentration is 162.7g/L.Then, the slurry pumping in the circulatory pool of the second stage is to the first step, and the slurry pumping in third stage circulatory pool is to the second stage, and third stage circulatory pool enters new slurry, proceeds reaction.The part not absorbed by slurry in first step absorption unit containing the tail gas of HCl flows into second stage absorption unit circulatory pool, in the absorption unit of the second stage, by slurry absorption portion, is not flowed into third stage absorption unit circulatory pool, Cl in the tail gas that third stage circulatory pool is discharged
2concentration be 10.56%(v/v).
Two. separation, neutralization, removal of impurities
Adopt press filtration separation to carry out separation to the slurry of deriving in first step absorption unit circulatory pool, gained filter residue washes with water, and washing lotion is returned to MnO
2breeze operation with slurry is used, and residue is abandoned.Gained filtrate (I) is used MnCO
3neutralization is 3.2 to pH.
Sampling records the Fe in filtrate
2+content be 10000ppm, according to Fe
2+3 times of molar weights, in filtrate, add MnS solid, then this filtrate is warmed up to 85 ℃, under 50 revs/min of agitation conditions, insulation was processed after 4 hours, sampling records Fe in filtrate
2+content be less than 2ppm, stop stirring.Above-mentioned filtrate is carried out to secondary filter with 0.5 μ m filter membrane, obtain filtrate (II).
Three. crystallization
Filtrate (II) is positioned in evaporating pan, is evaporated to MnCl in filtrate
2concentration be 820g/L, then under 50 revs/min of agitation conditions, be cooled to 30 ℃, stop stirring, then solid-liquid separation obtains MnCl
24H
2o crystallization.In the separated mother liquor of solid-liquid separation gained (III), add the NH that reacts molar weight
4hCO
3solid reacts, and then press filtration is separated, filter cake MnCO
3be cycled to used in filtrate (I) in and operation.
Four. recrystallization
By gained MnCl
24H
2o crystallization is made into the supersaturated solution of 90 ℃ with deionized water, under heat-retaining condition, solid-liquid separation obtains filtrate (IV), then under agitation condition, gained filtrate is cooled to 30 ℃, and then solid-liquid separation, vibra fluidized bed drying obtain MnCl
24H
2o crystallization 2#.
Embodiment 3
Adopt the higher-grade MnO that Mn content is 41.45wt%
2breeze is as raw material, and to be mixed with solid content be 300Kg/m
3slurry.Adopting the tail gas containing HCl of titanium sponge industry discharge is raw material, and this tail gas mainly comprises 24.17%(v/v) chlorine and hydrogenchloride, wherein chlorine is approximately 3-4%(v/v).
The present embodiment adopts three grades of absorption units, and the mode that ventage adopts lime solution to carry out water seal is sealed.The present embodiment technological process is as follows.
One. contain the absorption of the tail gas of HCl
The present embodiment adopts three grades of absorption units, and the mode that ventage adopts lime solution to carry out water seal is sealed.First in the first step circulatory pool of absorption unit, pass into the above-mentioned tail gas containing HCl, average flue gas flow 24000-27000Nm
3/ h, gas-liquid volume ratio example is controlled at 15L/Nm
3.Then ON cycle pump, by above-mentioned MnO
2slurry pumping is to first and second and three grades of circulatory pools of absorption unit.Control slurry and spray downwards, slurry and tail gas counter-current operation.Slurry in first step absorption unit circulatory pool is measured, and pH is 2 o'clock, and the slurry in first step absorption unit circulatory pool is exported, MnCl in gained slurry
2concentration is 282.0g/L.Then, the slurry pumping in the circulatory pool of the second stage is to the first step, and the slurry pumping in third stage circulatory pool is to the second stage, and third stage circulatory pool enters new slurry, proceeds reaction.The part not absorbed by slurry in first step absorption unit containing the tail gas of HCl flows into second stage absorption unit circulatory pool, in the absorption unit of the second stage, by slurry absorption portion, is not flowed into third stage absorption unit circulatory pool, Cl in the tail gas that third stage circulatory pool is discharged
2concentration be 15.58%(v/v).
Two. separation, neutralization, removal of impurities
Adopt press filtration separation to carry out separation to the slurry of deriving in first step absorption unit circulatory pool, gained filter residue washes with water, and washing lotion is returned to MnO
2breeze operation with slurry is used, and residue is abandoned.Gained filtrate (I) is used MnCO
3neutralization is 3.5 to pH.
Sampling records the Fe in filtrate
2+content be 15000ppm, according to Fe
2+3 times of molar weights, in filtrate, add MnS solid, then this filtrate is warmed up to 80 ℃, under 50 revs/min of agitation conditions, insulation was processed after 3 hours, sampling records Fe in filtrate
2+content be less than 2ppm, stop stirring.Above-mentioned filtrate is carried out to secondary filter with 0.5 μ m filter membrane, obtain filtrate (II).
Three. crystallization
Filtrate (II) is positioned in evaporating pan, is evaporated to MnCl in filtrate
2concentration be 840g/L, then under 50 revs/min of agitation conditions, be cooled to 32 ℃, stop stirring, then solid-liquid separation obtains MnCl
24H
2o crystallization.In the separated mother liquor of solid-liquid separation gained (III), add the NH that reacts molar weight
4hCO
3solid reacts, and then press filtration is separated, filter cake MnCO
3be cycled to used in filtrate (I) in and operation.
Four. recrystallization
By gained MnCl
24H
2o crystallization is made into the supersaturated solution of 90 ℃ with deionized water, under heat-retaining condition, solid-liquid separation obtains filtrate (IV), then under agitation condition, gained filtrate is cooled to 32 ℃, and then solid-liquid separation, vibra fluidized bed drying obtain MnCl
24H
2o crystallization 3#.
Through ultimate analysis, the results are shown in Table 1.
Table 1
| 1 # | 2 # | 3 # | |
| MnCl 2·4H 2O content % | 99.71 | 99.74 | 99.88 |
| K ppm | ＜10.0 | ＜10.0 | ＜10.0 |
| Na ppm | ＜10.0 | ＜10.0 | ＜10.0 |
| Ca ppm | 8.40 | 8.11 | 5.42 |
| Mg ppm | 6.47 | 5.90 | 3.21 |
| Fe ppm | ＜1.0 | ＜1.0 | ＜1.0 |
| Cu ppm | ND | ND | ND |
| Zn ppm | ND | ND | ND |
| Si ppm | ＜1.0 | ＜1.0 | ＜1.0 |
| Pb ppm | ND | ND | ND |
| As ppm | ND | ND | ND |
ND is not for detecting.
The present invention adopts the tail gas manganese dioxide reduction ore pulp material containing HCl, Cl in tail gas after processing
2concentration be 8.36-15.58%(v/v), reclaimed Cl
2, solved the recycling problem containing the tail gas of HCl.
From the results shown in Table 1, its MnCl of gained Manganous chloride tetrahydrate product of the present invention
24H
2o content is greater than 99.7wt%, K content < 10.0ppm, Na content < 10.0ppm, Ca content is 5.4-8.5ppm, Mg content is 3.2-6.5ppm, Fe content < 1.0ppm and Si content < 1.0ppm, meet lithium-ion secondary cell necessary requirement.Therefore, the present invention adopts the tail gas manganese dioxide reduction ore pulp material containing HCl, according to Fe
2+ionic weight adds manganese sulfide removal of impurities, has obtained highly purified Manganous chloride tetrahydrate product.
From the results shown in Table 1, gained Manganous chloride tetrahydrate products C a content of the present invention is 5.4-8.5ppm, and Mg content is 3.2-6.5ppm.Therefore, the present invention adopts dioxide ore for manganese to replace manganese carbonate ore, has solved manganese carbonate ore Ca, problem that Mg impurity is high, has obtained and has met the required high-purity Manganous chloride tetrahydrate product of lithium-ion secondary cell.
Claims (7)
1. a utilization is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, the method comprises:
First step, is passed into MnO by the tail gas containing HCl
2in slurry, react, stopped reaction when slurry pH is 1-2, and control reaction stops MnCl in disposed slurry
2concentration be 100-300g/L, contain Cl after reclaiming reaction simultaneously
2gas; Described tail gas and MnO containing HCl
2the gas-liquid volume ratio example of slurry is controlled at 12-15L/Nm
3;
Second step, obtains the first filtrate by first step gained slurry solid-liquid separation, and then in gained the first filtrate, adding alkaline substance containing manganese to be neutralized to pH is 3-3.5, then removal of impurities, filters and obtains the second filtrate;
Third step, carries out crystallization, recrystallization processing by the second filtrate, obtains MnCl
24H
2o product;
Described MnCl
24H
2mnCl in O product
24H
2o content is greater than 99.7wt%; K content < 10.0ppm, Na content < 10.0ppm, Ca content is 5.4-8.5ppm, Mg content is 3.2-6.5ppm, Fe content < 1.0ppm and Si content < 1.0ppm.
2. utilization according to claim 1 is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, and it is characterized in that, in first step, described MnO
2the solid content of slurry is 300-350kg/m
3.
3. utilization according to claim 1 and 2 is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, and it is characterized in that, in first step, adopt three grades of absorption cycles to react.
4. utilization according to claim 1 is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, and it is characterized in that, in second step, described removal of impurities comprises: with Fe in filtrate
2+molar weight meter, adds the MnS of 3 times of molar weights, then described the first filtrate is warmed up to 80-90 ℃, and insulation is processed to Fe
2+content be less than 2ppm.
5. utilization according to claim 1 is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, and it is characterized in that, described crystallisation step comprises: second step gained the second filtrate is evaporated to MnCl
2concentration be 800-840g/L, be then cooled to below 35 ℃, solid-liquid separation obtains MnCl
24H
2o crystallization.
6. utilization according to claim 5 is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, and it is characterized in that, described re-crystallization step comprises: by crystallisation step gained MnCl
24H
2o crystallization is made into the supersaturated solution of 90 ℃, and under heat-retaining condition, solid-liquid separation obtains the 4th filtrate for the first time, then gained filtrate is cooled to below 35 ℃, follows solid-liquid separation, the dry MnCl that obtains for the second time
24H
2o crystallization.
7. utilization according to claim 5 is containing the tail gas recycle Cl of HCl
2and prepare the method for Manganous chloride tetrahydrate, and it is characterized in that, in the mother liquor that the solid-liquid separation of described crystallisation step obtains, add the NH that reacts molar weight
4hCO
3solid reacts and obtains MnCO
3, and by described MnCO
3be applied to the neutralization procedure of the first filtrate.
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| CN103641748B (en) * | 2013-11-29 | 2016-02-24 | 湖北星火化工有限公司 | A kind of recycle by-product hydrochloric acid prepares the method for methylsulphonic acid |
| CN104860268A (en) * | 2015-06-04 | 2015-08-26 | 中南大学 | Method for cyclic utilization of chlorine gas and coproduction of manganese chloride in chloride pyridine production process |
| CN104961160B (en) * | 2015-06-26 | 2016-08-24 | 重庆新申新材料股份有限公司 | A kind of production method of granular anhydrous manganese chloride |
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